Control of acarinae with carbamates having an oxime ether function

ABSTRACT

WHEREIN R1, R2, R3 and X have the meanings given below. Said oxime ethers are used in herbicidal preparations for controlling undesired plant growth in cultures of cereals, maize, rice and soya. Some of these ethers can also be used for combatting pests of the order acarinae.   The invention relates to new oxime ethers of the formula

United States Patent Hubele Dec. 24, 1974 CONTROL OF ACARINAE WITH [56] References Cited CARBAMATES HAVING AN OXIME ETHER UNITED STATES PATENTS FUNCTION 3,492,333 1/1970 Dickore 260/472 Inventor: Adolf Hubele, Riehen near Basel,

Switzerland Assignee: Ciba-Geigy, Limited A. G., Basel,

Switzerland Filed: Aug. 24, 1973 Appl. No.: 391,442

Related US. Application Data Division of Ser. No. 195,822, Nov. 4, 1971, Pat. No. 3,772,385, which is a continuation-in-part of Ser. No. 786,762, Dec. 24, 1968, abandoned.

Foreign Application Priority Data Jan. 5, 1968 Switzerland 121/68 US. Cl 424/300, 260/472, 260/482 C, 71/106, 71/111 Int. Cl A01n 9/20 Field of Search 260/472; 424/300; 71/106, 71/111 Primary Examiner-Vincent D. Turner Attorney, Agent, or FirmFrederick H. Rabin [57] ABSTRACT The invention relates to new oxime ethers of the formula 3 Claims, No Drawings CROSS REFERENCE This is a division of application Ser. No. 195,822, filed on Nov. 4, 1971, now US. Pat. No. 3,772,385, which in turn is a continuation-'in-part of application Ser. No. 786,762 filed on Dec. 24, 1968, now abandoned.

The present invention relates to active substances for compositions for controlling undesirable plant growth in cultures of useful plants, such as cereals, maize, rice and soya and some of these compounds are also useful for combatting pests of the order acarinae (mites, ticks etc.).

The active substances are compounds of the formula I wherein R, is a lower alkyl radical, with one to four carbon atoms, which is unsubstituted or substituted by a chlorine atom, a phenyl radical that is unsubstituted or mono to trisubstituted by members of the group consisting of halogen atoms, methyl, methoxy, trifluoromethyl or nitro groups, or R, is the benzyl phenylethyl or cyclohexyl radical;

R is a nitro, formyl, methoxycarbonyl or di-lower alkyl sulfamyl radical, wherein the lower alkyl groups have one to four carbon atoms;

R, is a hydrogen or chlorine atom, a lower alkyl, lower alkoxy group with one to four carbon atoms, the methoxycarbonyl or di-methylsulfamyl group and X are identical and represent chlorine, bromine or iodine atoms.

In these definitions under lower alkyl groups with one to four carbon atoms, the straight chained or branched radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. butyl and tert.butyl are understood.

The present invention claims the new oxime-ethercarbamates of formula I.

The invention at the same time claims pesticides which contain compounds of formula l as active substances together with suitable carriers.

The new compounds are produced by known methods according to following indication:

The starting products of formula [I X NO;

I X 7 R3 (II) which are necessary for the manufacture of the compounds of formula I can be manufactured in a simple manner, for example from 3,5-dihalogeno-4-hydroxybenzyldoxime and an appropriately substituted chlorobenzene of formula in alkaline solution.

If these compounds of formula II are to be converted to esters of general formula I then, provided the reaction is not too drastic, all usual esterification methods can be applied to the conversion of the phenolic OH group. In order to ensure mild conditions, it is a ppropriate to start from the phenolate and to react with appropriate carboxylic acid halides. It is also possible to produce the phenylester grouping at temperatures in the range of 0 to C with carboxylic acids or carboxylic acid anhydrides, with acid esters or lactones or in individual cases also with ketenes.

For converting the starting products ll to the corresponding carbamates, the phenolic OH group can be reacted according to usual methods with isocyanates of the type R, NCO

or with compounds which can transiently form these isocyanates, or also with carbamic acid chlorides of the type R, NH COCl or of the type R, N(CH COCl It is however also possible first to manufacture the corresponding phenolchlorocarbonate from the OH group by means of COCl and then to allow this, where possible, to react with an amine R,-NH or R,N- HCH R, in each case has the significance given forformula l. Possible solvents are generally acetonitrile, ether, dioxane, dimethylformamide, dimethylsulphoxide and others.

The herbicidal selectivity in varieties of grain, maize and rice on the one hand and in leguminosae (peas, beans, soya beans, clover andlucerne) on the other, on post-emergent treatment, follows for all compounds of formula I from the field of use initially quoted, though to different extents. Particularly outstanding representatives are those of general formula III Continued COOCH3 /CHa SO2-N Alkyl o 2 O o Q Z If? O Alkyl The acaricidal action of a series of representatives of formula I, which has been observed against all kinds of representatives of the order Acarina such as ticks, mites, spinning mites and the like, should also be emphasised. Here it is worth mentioning that the amounts used can be chosen at an order of magnitude which lies below any influence on the plants.

Typical representatives of this are compounds of formula lll wherein Ar denotes the group U.S. Pat. No. 3,329,702 or British Pat. No. 1,047,644 or Swiss Pat. No. 424,359.

In many cases it is advantageous to use granules to achieve uniform release of active substances over a longer period of time. These granules can for example be manufactured by dissolving the active substance in an organic solvent, absorbing this solution by a granulated material, for example Attapulgite or SiO. and removing the solvent.

In the form of one or other use such materials can also be applied by distribution over large areas (spraying, dusting and the like) by means of aircraft.

The various use forms of such materials can be more closely suited to the end uses in the usual manner by adding substances which improve the distribution, adhesion, rain resistance and possibly the penetrating power, such as for example fatty acids, resins, wetting agents, glue, caseine or alginates.

In the manufacture of herbicidally active materials there are furthermore numerous possible components for use in combinations, of which the most important representatives are quoted below: N-phenyl-N, N-dimethylurea, N-p-chlorophenyl-N', N'-dimethylurea, N-3,4-dichlorophenyl-N', N- dimethylurea, N-3,4-dichlorophenyl-N'-methoxy-N'- methylurea, N-4-bromo-3-chlorophenyl-N'-methoxy- N'-methylurea, trichloracetic acid, 2,6- dichlorobenzonitrile, 2,3,6-trichlorobenzoic acid, 2,4- D, 2-,4,5-T, MCPB, MCPP, isopropyl-carbanilate, isopropyl-3-chlorocarbanilate, N-3-chlorophenylcarbamic acid 4'-chlorobutin-2-yl-l-ester, 2,3,6-trichlorophenylacetic acid and salts, 2-chlorodiallylacetamide, 2-chloro-4,6-bis-ethylamino-s-triazine, 2-methoxy-4,6- bis-ethylamino-s-triazine, 2-azido-4-methyl-thio-6- isopropylaminotriazine, the monomethylarsenate di-Na salt, various arsenites, Na metaborate, Na chlorate and sulphamic acid.

When using the materials against ectoparasites on farm animals such as cattle, sheep, goats and others, it is advantageous to use dipping baths in which the active substances are present alone or, as described, in an emulsified or dispersed form.

In the following text the parts denote parts by weight.

[Compound 361 parts of 3,5-dibromo-4-hydroxybenzaldoxime-O- 2',4'-dinitrophenyl ether are suspended in 800 parts by volume of ethyl acetate whilst stirring and 41 parts of 4-chlorophenylisocyanate in 200 parts by volume of ethyl acetate are added at 50 C. The weakly exothermic reaction is initiated by adding 0.l parts of triethylene diamine. After standing for 4 hours at room temperature the mixture is filtered and the product digested with hot acetonitrile and again filtered. Melting point: l94l95 C (decomposition).

The following compounds of the type of are obtained in an analogous manner.

Melting point, C.

Compound No. R1 (decomposition) HaC Continued Melting point, C Compound No. R1 (decomposition) 22 O C H: 164-168 The following compounds of the type of are obtained in an analogous manner.

Melting point, 0.

Compound N 0. R1 (decomposition) 27 OH 205-206 C2H5- 198-199 n-CaH7 196-197 1so-C 311 193-196 C4Ho 186-187 32 lCHz-CHz- 195-196 Q 180-182 39 (IJFQ 177-179 C Fs- Continued Continued Melting point, C Melting point, C. Compound No. R1 (decomposition) Compound No. R1 (decomposition) i 58 H 107-100 Q 5 CHa- 45 (Ill ([3111 186- 88 61 Cl 203-204 47 (llHa -176 63 01 134.13

| C CH:1-

66 CF; 178-181 in a similar manner the compound of formula N 50 CF O. c

Bl N02 033 l I 07 ('11 103-10.:

NCOOCH=NO@NO2 u. CH3 l Br Melting point LBS-160 [decomposition] 40 Cl is obtained by reacting the Na salt of 3,5-dibromo-4- The followmg Compounds of the: type of hydroxybenzaldoxime-O-Z',4'-dinitrophenyl ether with dimethylcarbamoyl chloride.

The followin com ounds of the t e of g p yp R1-NHCOO CH:NOC1IO I No: Br

R1NHCO-O CH=N-O NO2 I are obtained in an analogous manner 22. 1 7n 2. to. 2

Melting point, C. are obtained in an analogous manner to that which has Compound Q been described for the manufacture of compound 36. 68 on? 108-100 Melting point, C. 70 179-180 Compound No. R, (decomposition) 207-208 202-204 71 2. on 182-184 -200 I I 206-207 Q 207-208 60 Continued Melting point, 0. Compound No. R1 (decomposition) The following compounds are obtained in an analogous manner Melting point 173-174 C.

(decomposition) The following eotnpounds of the type of Cl IP: RuNHuWOQoHW M are obtained in an analogous manner Melting point, 0.

The following compounds of the type of I N02 5 R1NHCOOOH=NO NO2 are obtained in an analogous manner Melting point, C. Compound No. R1 (decomposition) 86 CH3- 209-210 a7 olomom- 200-207 80 OF; 186-188 Q The following compounds of the type of Cl N02 0113 R1-NIIC 0-.0- -CH:N-O- -s 0i-N CH: G1

are obtained in an analogous manner Melting point C. 40 Compound No. R1 (decomposition) 92 oHl -181 The following compounds of the type of The following compounds of the type of are obtained in an analogous manner Melting point, C. Compound No. R; (decomposition) 97. CHa- 182-183 C1-C Hr-CHz- I 170-172 The followingcompounds of the type of are obtained in an analogous manner Melting point, C.

Compound No. R1 (decomposition) The following compounds of the type of Br RiNH-COO -CH=NO o 1B! V are obtained in ananalogous manner Melting point, Q o Compound N 0. R1 (decomposition) 106 Cl--CH2CH2 189-190 107 CaHs- 184-185 Continued Melting point, 0. Compound No. R, (decomposition) 111 ."I'.... inc 163-164 The following compounds of the type of Br m-Nn-oo-o--on=N-o--oooom I Br I are obtained in an analogous manner Melting point, 0.

The following compounds of the type of are obtained in an analogous manner Melting point, C.

Compound No. R1 (decomposition) 118 CH 181-182 119 C1CH2-CHz- 148-14515 v13 14 Cntinued the following instructions: 20 parts of active substance,

Melting point, C. 7 parts of xylene and 10 parts ofa mixture of a reac- Compound No. In (decompositlon) t1on product of an alkylphenol w1th ethylene ox1de and 2 EE calcium dodecylbenzene-sulphonate are mixed. On di- Q 5 lution with water to the desired concentration a sprayable emulsion results. CF31 125 175.17 EXAMPLE 3 a Q Selectwe herblcldal actlon m EXAMPLE 2 10 The compounds encompassed by formula 1 show a good action in combatting dicotyledon plants in the Examples of Formulations post-emergent treatments. Dusting Agents The treatment of the experimental field with active Equal parts of an active substance according to the substances according to the invention is carried out 12 invention and of precipitated silica are finely ground. 15 days after sowing, when the plants have developed one Dusting agents which preferably contain l-6 7c of acto two new leaves after emerging. The amounts used tive substance can be manufactured therefrom by mixare 2, 1 and 0.5 kg of active substance per hectare. ing with kaolin or talc. The results are presented in the three tables which Spraying Powders follow. As shown by the results, the compounds menln order to manufacture a spraying powder the foltioned are throughout suitable for combatting dicotylelowing components are for example mixed and finely don plants in varieties of grain. Wheat, barley, oats and ground: 50 parts of active substance according to the maize are completely spared by almost all compounds. present invention, 20 parts of Hisil (highly adsorptive Some compounds are tolerated by soya and flax culsilica), parts of bolus alba (Kaolin), 3.5 parts of a tures. The compounds 27, 33, 35, 38, 39, 40, 49, 72, reaction product of p-tert. octylphenol and ethylene 25 73, 113, 114, 116 and 118 are tolerated by rice. The oxide and 1.5 parts of sodium l-benzyl-Z-stearylactive substances 89 and 91 only affect rice plants benzimidazole-6,3-disulphonate. slightly but destroy the well-known rice weed Panicum. Emulsion Concentrate The following ratings are applicable to the, assess- Easily soluble active substances can also be formument in the tables: 1-2 no action, 3-4 slight damlated as an emulsion concentrate in accordance with age, 5-7 severe damage and 8-9 plant died.

Table 1 Variety Com- Com- Com- Com- Com- Com- Com- Com- Com- Comf pound pound pound pound pound pound pound pound pound pound Pla No. No. No. No. No. No. No. No No. No. 27 33 35 36 37 38 39 41 47 49 Triticum l l 1 l l 1 l l l l Hordeum l l l l 1 l l l l l Zea 1 1 1 1 1 1 1 1 1 1 Oryza 2 1 1 3 3 1 1 4 3 1 Sorghum l l l l l l l l 2 l Panicum 3 l l 3 I 1 l 2 l 1 Beta vulg. 9 9 9 9 9 9 9 9 9 9 Galium 9 9 4 9 6 9 s 9 9 3 Calendula 9 9 9 9 9 9 9 9 9 9 Alopercurus Chrysanthemum 9 9 9 9 9 9 9 9 9 9 Linum 5 2 1 4 2 3 I 3 2 4 2 Brassica 9 9 9 9 9 9 9 9 9 5 Ipomoea 4 3 5 8 6 4 3 6 5 2 Daucus 5 3 5 8 6 5 3 6 5 l Soya 3 3 2 4 2 2 2 2 3 1 Use amounts: 1 kg of active substance/hectare Table 1a Variety of cpd. cpd. cpd. cpd. cpd. cpd. cpd. cpd. cpd. cpd. cpd. cpd. cpd. Plant 29 31 34 44 45 46 4s 51 53 54 55 57 5x Triticum l l l l l l l l l l l l l Hordeum 1 l l l l l l l l l l l l- Avena 1 1 1 1 1 1 1 1 1 1 1 1 1 Zea 1 1 1 1 1 1 1 1 1 1 1 1 1 Oryza 4 l l l 2 l l l 4 5 3 l 3 Digitaria 1 1 1 1 1 1 1 1 1 1 1 1 1 Sorghum l l l l l l l l 3 2 2 l 2 Panicum 1 l l 2 1 lv 1 l 3 2 l l 4 P021 1 1 1 1 1 1 1 1 1 1 1 1 1 Alopecurus 1 l l l l l l l 2 l 2 l l Cyperus veg. l l l l l l l l l l l l l Cynodon veg. l l l l l l l l l l 1 l 1 Beta 9 9 9 9 9 9 9 9 9 9 9 9 9 Galium 9 6 5 7 9 4 4 7 5 5 3 3 4 Calendula 9 9 5 9 9 9 7 5 5 6 4 9 9 Chrysanthemum 9 9 9 9 9 6 7 8 8 9 9 9 9 Linum 1 3 4 3 2 3 9 1 4 5 7 5 x 7 Brassica 9 9 9 9 9 l 9 8 9 9 9 9 9 Continued 0.5 kg of active 1.0 kg of active substance/hectare substance/hectare Comp- Chry- Chrypound Trit- Hor- Av- Zea Or- Calesant- Li- Bras- Stel- Soja CaIesant- Li- Bra SteI- Soju No. icum deum ena yza nduIa hemum num sica Iaria ndula hemum hum sicu laria 72 l I I I Z 9 9 6 9 9 5 9 9 4 9 7 4 I I3 3 I I I I 9 9 4 9 9 4 9 9 3 9 9 3 I I4 I I I I I 9 9 3 9 9 3 9 9 3 9 9 3 I I6 3 l 3 I l 9 9 3 9 9 3 9 9 3 9 9 3 I I8 I I I I I 9 9 5 9 9 4 9 9 3 9 9 3 I I9 I I I I 3 9 9 6 9 9 3 9 9 5 9 9 3 I20 I I I I 3 9 9 4 9 9 3 9 9 4 9 9 2 I2I I I I I 3 9 9 7 9 9 3 9 5 6 9 9 2 I22 I I I I 3 9 9 5 9 9 4 9 9 4 9' 9 3 I23 I 4 I I 3 9 9 4 7 9 4 9 9 4 7 9 3 I24 I I I I 3 9 9 6 9 9 5 9 9 4 6 9 4 I25 I I I I 3 9 9 4 9 9 4 9 9 4 9 9 3 2 kg. of active substance/hectare Compound Trit- Hor- CaIen- Chrysannumbet mum deum Avena Zea Oryza Soja Galium dula themum Linum Bmssica 1 kg. of active substance/hectare Compound Trit- Hor- Calen- Chrysannumber icum deum Avena Zea Oryza Soja Galium dula themum Linum Brassica For comparative purposes the results obtained in this test with previously known substances with partly similar chemical structure are shown in Table .II.

The compounds thus tested are methyl-3,4-dichIoro-carbanilate known from the US. Pat. No. 3,116,995 and 5 isopropyI-N-(3-chlorophenyl)carbamate, known under the tradename CIPC.

Variety of plant Amo compound unl applied in kg/ha Triticum Hordeum Avena Zea Oryza Digitaria Sorgum Panicum Poa Alopecurus Cyperus veg, Cynodon veg. Beta Galium Calendula Chrysanthemum Linum Sinapis Brassica Ipomoea Stellaria 'Soya Gossypium Amaranthus EXAMPLE 4 EXAMPLE 5 Several compounds of the present application were In order to test the acaricidal action, phaseolus plants compared in a field test with the compound in the two-leaf stage are infested, 12 hours before the NO treatment, by placing pieces of leaf attacked by spin- (A) ning mites on them. After 12 hours a population in all 0 stages of development is present on the test plant. HOQTCELNO G The active substance No. 75was sprayed in the form of an emulsion onto the plant through a fine atomiser in such a way that a uniform deposit of droplets was produced on the surface of the leaf. After 7 days the know from the French 1,494,078- mortality was determined and expressed as a percentl p e Small lots were Seeded with the (3111- age. The following mortality values were determined tllfe P, P y Summer and Winter he TWO for two varieties of spinning mite after 2 and 7 days:

weeks after sowing, when the plants had reached the 2 3 leaf stage, they were sprayed with the testing liquor, 15 Termychus so that the final amount of active substance applied Conga. Adults Lame Eggs corresponded to 1 respectively 2 kg per hectare. The testing liquor consisted of a 1% sprayable disper- [ppm] 2 Days 7 Days 2 Days 7 Days 7 Days 800 100% 8071 100% x0% 00% s on obtained from the following composition by dilu 400 80% 80% 8071 80% 60% tion with water: 200 60% 0% 60% 00% 0% 100 0% 0% 0% 50% of one of the active compounds to be tested b) Temnychus mam 33.5% of Bolus alba (kaolin) Concen- Adults Larvae Eggs tration ll% of the ammonium salt of ligninsulfonic acid [ppm]. 2 Days 7 Days 2 Days 7 Days 7 Days 4.5% of sodium dinaphtylmethanedisulfonate (prodpct commercially available under the tradename 400 80% 80% 0W 8W 6W Neradol 200 6071 00% 80% 60% 00% The assessment of the test was made 4 weeks after the treatment and the plants were evaluated according to the following y What we claim is:

l. A method for combating pests of the order acarinae comprising applying to sites infested with such pests an acaricidally effective amount of a compound note: crop: weed: of the formula I (optimum) no damage. plants killed X N02 as control I l 2 4 slight coverable heavy damage damage R1NHC0-O CH=NO- N02 5 8 heavy irreversible slight recoverable damage da ag X lower alkyl 9 plant killed no damage. same as 40 wherein R, is lower alkyl with one to four carbon atoms which is unsubstituted or substituted by a chlorine T I h I H atom, phenyl which is unsubstituted or mono to trisube l Elven t e f0 lowmg ta stituted by members selected from the group consisting hote glvehfm the ahothef for the evalu' of halogen, methyl, methoxy, trifluoromethyl and nitro, ation of the weeds in that particular lot tn general and or R is benzyl, phenylethyl or cyclohexyl; and X repreathird one for theproble rnye din eachindividual lot. sents chlorine, bromine or iodine.

compound tested A 65 40 63 64 92 concentration applied in kg/ha 1 In these field tests, in post emergence application of 2. The method according to claim 1 wherein the pests 1 and/or 2 kg per hectare, the compounds of the presare ticks or mites. ent application show selective herbicidal activity in 3. The method according to claim 1 in which the crops of soya and excellent selective herbicidal activity compound is i cro a. P5 of summertime win e wheat Br N02 Thecompound A according to the French Pat. No. 1,494,231 shows in the same tests no selective herbi- 4102 c1dal activity in soya and though it is very compatible towards wheat, its weed controlling ability is not satis- F3 1 Br, CH3 factory. 

1. A METHOD FOR COMBATING PESTS OF THE ORDER ACARINAE COMPRISING APPLYING TO SITES INFESTED WITH SUCH PESTS AN ACARICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method according to claim 1 wherein the pests are ticks or mites.
 3. The method according to claim 1 in which the compound is 